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Symmetry Operations
1. E . The identity operation. This operator leaves the object unchanged.
2. C n . The proper rotation operator. This operator performs a counterclockwise
2
rotation about an axis through the center of mass by an angle of . For example, C 3 rotates
n
by 120; C 32 by 240; and C 31 by 120. Note the operator equalities C 32 C 31 and C 33 E .
The operator C 4 rotates by 90 and C 2 by 180. Therefore, C 42 C 2 . If the object has several
rotation axes, the axis with the highest order (largest n) is the principal axis. Usually, the center
of mass of the molecule is located at the origin of the Cartesian coordinate system, and the
principal axis is aligned with the z axis. When several C n axes have the same order, the z axis is
taken along the one passing through the greatest number of atoms.
3. i . The inversion operation. This operator projects the object through the center of
symmetry to an equal distance on the other side of the center.
4. h . The horizontal mirror plane reflection. The mirror plane is perpendicular to a
principal C n axis. This operator reflects the object across the plane of symmetry.
5. v . The vertical mirror plane reflection. The mirror plane contains a principal C n
axis. This operator reflects the object across the plane of symmetry.
6. d . The dihedral (or diagonal) mirror plane reflection. The mirror plane contains a
principal C n axis and bisects the angle between two horizontal C 2 axes. (These horizontal C 2
axes are perpendicular to the principal C n axis.) The operator reflects the object across the
plane of symmetry.
7. S n . The improper rotation operator. This operation performs a counterclockwise
2
rotation about an axis by an angle of followed by a reflection across a mirror plane
n
perpendicular to that axis. In other words, this is a C n rotation followed by reflection across a
h mirror plane.
S n
h C h
If an object has C n and
h as symmetry elements, then it must also have S n as
symmetry element. However, it is possible for S n to be a symmetry element for an object when
C and h are not symmetry elements.
n
Point Groups
If two symmetry operations are symmetry elements of an object, then their product is also
a symmetry element. Any set of operations for which any product of members of that set is a
member of the set is called a group. Group theory is the study of the mathematical properties of
such a collection of symmetry elements. Groups containing only symmetry elements that leave
one point in the molecule unchanged are called point groups. In addition, crystals also have
symmetries arising from translation through space and are called space groups. However, here
we consider only point groups. Each distinct group of symmetry elements has a name.
We now present the Schoenflies naming system for point groups:
Dihedral Groups
D n . Contains the symmetry elements E , C , and n C axes perpendicular to C .
n 2 n
Note that for n = 2, the group has three mutually perpendicular C 2 axes.
D nh . Contains the symmetry elements E , C ,n C axes, and h (mirror plane is
n 2
perpendicular to the principal axis). This group also has n vertical mirror planes and i if n is an
even number.
D nd . Contains the symmetry elements E , C ,n C
n
axes, and n vertical mirror planes
2
d . This group also has an improper axis of double order S 2 n parallel to C and i if n is an
n
odd number.
Linear Groups
These groups are special cases of the above groups for n (i.e. operation about the
axis by any angle is symmetry element).
C v . This group is linear unsymmetrical. For example, HCl and HCN.
Dh . This group is linear symmetrical. For example, CO 2 .
Cubic groups
Td . This group has the symmetry of a regular tetrahedron. For example, CH 4 .
O h . This group has the symmetry of a regular octahedron.
2
I h . This group has the symmetry of a regular icosahedron. For example, B12 H 12 .
The groups D nh and D nd are often difficult to distinguish. Both have C n , n C 2 , and n
mirror planes. D nh has a horizontal mirror plane h as well as vertical mirror planes (
v,
each axis). But for the D nd groups, the vertical mirror planes lie
v plane contains a C 2
Further discussions of these topics are found in Mortimer pages 651-655, 682-689, 707.